CN112029097B - Polyimide film, preparation method thereof and flexible display panel - Google Patents

Polyimide film, preparation method thereof and flexible display panel Download PDF

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CN112029097B
CN112029097B CN202010875020.9A CN202010875020A CN112029097B CN 112029097 B CN112029097 B CN 112029097B CN 202010875020 A CN202010875020 A CN 202010875020A CN 112029097 B CN112029097 B CN 112029097B
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CN112029097A (en
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汪亚民
陈诚
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Wuhan China Star Optoelectronics Semiconductor Display Technology Co Ltd
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Abstract

Provided are a method for manufacturing a polyimide film and a polyimide film manufactured by the manufacturing method. The manufacturing method comprises the following steps: dissolving porphine nickel (II) in trifluoroacetic acid to carry out nitration reaction with a nitrating agent to generate dinitroporphine nickel (II); reacting the dinitroporphine nickel (II) with a hydrazine salt to form diaminoporphine nickel (II); polymerizing the diaminoporphyrin nickel (II) with a halogen-containing dianhydride to form a polyimide precursor; and subjecting the polyimide precursor to intramolecular condensation to form a polyimide film.

Description

Polyimide film, preparation method thereof and flexible display panel
Technical Field
The application relates to the field of materials, in particular to a polyimide film, a preparation method thereof and a flexible display panel.
Background
In the field of OLED panels, one commonly used flexible substrate uses a polyimide film. The known polyimide film material on the market generally has difficulty in combining the mechanical property, the thermal property and the optical property. The mechanical properties of the existing polyimide film are evaluated by tensile properties, as basic requirements, the maximum breaking stress of a polyimide film with the thickness of 10 mu m reaches 350MPa or more, the breaking elongation reaches more than 15%, the thermal properties are evaluated by a thermogravimetric Analysis (TGA), the temperature of weight loss percentage mass of the polyimide film is above 560 ℃, the thermal expansion coefficient is within 5ppm/K, and meanwhile, the transmittance in the optical property aspect can reach more than 75% within the range of 380 nm-780 nm.
Disclosure of Invention
The purpose of the present invention is to provide a polyimide film having mechanical properties, thermal properties, and optical properties.
The application provides a method for manufacturing a polyimide film, which comprises the following steps:
dissolving porphine nickel (II) in trifluoroacetic acid to carry out nitration reaction with a nitrating agent to generate dinitroporphine nickel (II), wherein the porphine nickel (II) is the following compound (1) and derivatives thereof:
Figure BDA0002652378560000011
wherein the group R is selected from-H, alkyl, alkoxy, alkenyl, carbonyl, carboxyl, hydroxyl, amido, halogen, biphenyl, heterocyclic radical, phenyl or tolyl;
reacting the dinitroporphine nickel (II) with a hydrazine salt to form diaminoporphine nickel (II);
polymerizing the diaminoporphyrin nickel (II) with a halogen-containing dianhydride to form a polyimide precursor, wherein the halogen-containing dianhydride is the following compound (2):
Figure BDA0002652378560000021
wherein, the group R1 is a cyclic alkyl group or an aromatic group containing halogen; and
subjecting the polyimide precursor to intramolecular condensation to form a polyimide film.
In one embodiment, the step of dissolving porphine nickel (II) in trifluoroacetic acid to react with a nitrating agent to form dinitroporphine nickel (II) comprises: dissolving the porphine nickel (II) in a solvent, gradually dropwise adding a nitrating agent, and reacting to generate the para-nitro porphine nickel (II).
In one embodiment, the step of dissolving porphine nickel (II) in trifluoroacetic acid to react with a nitrating agent to form dinitroporphine nickel (II) comprises: dissolving the porphine nickel (II) in a solvent, and adding a nitrating agent at one time to react to generate the ortho-porphine nickel (II).
In one embodiment, the step of reacting the dinitroporphine nickel (II) with a hydrazine salt to form the diaminoporphyrine nickel (II) comprises: under the protection of argon, dissolving dinitroporphin nickel (II) by using a solvent, heating to 40-60 ℃, slowly adding hydrazine salt, raising the temperature to 75-100 ℃, and reacting for 12-30 h to generate the diamino porphin nickel (II).
In one embodiment, the group R1 is selected from a halogen atom or a halomethyl substituted cyclobutyl, phenyl, biphenyl, benzhydryl.
In one embodiment, the step of subjecting the polyimide precursor to intramolecular condensation to form a polyimide film comprises: and dissolving and filtering the polyamic acid precursor, coating the filtrate on a glass substrate, placing at high temperature under vacuum to remove the solvent, baking at high temperature to form a film, soaking in deionized water, separating and drying from the glass substrate to obtain the polyimide film.
The present application also provides a polyimide film selected from the following compounds:
Figure BDA0002652378560000031
or
Figure BDA0002652378560000032
Wherein the group R is selected from-H, alkyl, alkoxy, alkenyl, carbonyl, carboxyl, hydroxyl, amido, halogen, biphenyl, heterocyclic radical, phenyl or tolyl;
the group R1 is a cyclic hydrocarbon group or an aromatic group containing halogen.
In one embodiment, the group R1 is selected from a halogen atom or a halomethyl-substituted cyclobutyl, phenyl, biphenyl, benzhydryl.
In one embodiment, the polyimide is:
Figure BDA0002652378560000041
or
Figure BDA0002652378560000042
The present application also provides a flexible display panel comprising a flexible substrate comprising the polyimide film as described in any one of the above.
Polyimide films are prepared using diamines containing a porphine nickel (II) structure as a starting material. When porphine nickel (II) is catalytically hydrogenated in a common solvent, porphine nickel (II) is preferentially hydrogenated, but the benzene ring is preferentially hydrogenated in trifluoroacetic acid. According to the preparation method, a nitrating agent is introduced into trifluoroacetic acid to synthesize nitrated porphin nickel (II), hydrazine salt is utilized to prepare diamine containing porphin nickel (II), then a dianhydride structure containing halogen is introduced to generate a polyimide precursor, and the polyimide precursor is crosslinked and cured at a high temperature to finally obtain the polyimide film material with excellent heat resistance, mechanical properties and optical properties.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1(a) to 1(d) are temperature profiles of the polyimide film curing provided in the present application.
FIG. 2 is a nuclear magnetic spectrum of a polyimide film of example 1 of the present application.
FIG. 3 is a graph showing the tensile properties of the polyimide films of examples 1 and 2 of the present application.
Fig. 4 is a graph showing the weight loss on heating of the polyimide films of examples 1 and 2 of the present application.
Fig. 5 is a graph showing the results of a light transmittance test of the polyimide films of examples 1 and 2 of the present application.
Fig. 6 is a schematic structural diagram of a flexible display panel according to an embodiment of the present disclosure.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. It should be apparent that the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A first embodiment of the present application provides a method for manufacturing a polyimide film, including the steps of:
s1: dissolving porphine nickel (II) in trifluoroacetic acid to carry out nitration reaction with a nitrating agent to generate dinitroporphine nickel (II), wherein the porphine nickel (II) is the following compound (1) and derivatives thereof:
Figure BDA0002652378560000051
wherein the group R is selected from-H, alkyl, alkoxy, alkenyl, carbonyl, carboxyl, hydroxyl, amido, halogen, biphenyl, heterocyclic radical, phenyl or tolyl.
It is understood that other sites on the porphine nickel (II) ring may also be substituted.
Since porphine nickel (II) is hydrogenated catalytically in a common solvent, porphine nickel (II) is preferentially hydrogenated, but the benzene ring is preferentially hydrogenated in trifluoroacetic acid. The nitrated porphine nickel (II) can be synthesized by introducing a nitrating agent into trifluoroacetic acid. In addition, para or ortho porphine nickel (II) may be synthesized by controlling the addition of the nitrating agent. The nitrating agent used in this step may be potassium nitrate, calcium nitrate, ammonium nitrate, concentrated nitric acid, or the like.
In one embodiment, the step of dissolving porphine nickel (II) in trifluoroacetic acid to react with a nitrating agent to form dinitroporphine nickel (II) comprises: dissolving the porphine nickel (II) in a solvent, gradually dropwise adding a nitrating agent, and reacting to generate the para-nitro porphine nickel (II).
The chemical reaction that takes place in this step is:
Figure BDA0002652378560000061
in one embodiment, the step of dissolving porphine nickel (II) in trifluoroacetic acid to react with a nitrating agent to form dinitroporphine nickel (II) comprises: dissolving the porphine nickel (II) in a solvent, and adding a nitrating agent at one time to react to generate the ortho-porphine nickel (II).
The chemical reaction that takes place in this step is:
Figure BDA0002652378560000062
s2: reacting the dinitroporphine nickel (II) with a hydrazine salt to form the diaminoporphyrine nickel (II).
In one embodiment, the hydrazine salt may be selected from hydrazine hydrochloride, hydrazine sulfate, hydrazine hydrobromide, and the like.
In one embodiment, the step S2 includes: under the protection of argon, dissolving dinitroporphin nickel (II) by using a solvent, heating to 40-60 ℃, slowly adding hydrazine salt, raising the temperature to 75-100 ℃, and reacting for 12-30 h to generate the diamino porphin nickel (II).
The chemical reaction that takes place in this step is:
Figure BDA0002652378560000071
or
Figure BDA0002652378560000072
S3: polymerizing the diaminoporphyrin nickel (II) with a halogen-containing dianhydride to form a polyimide precursor, wherein the halogen-containing dianhydride is the following compound (2):
Figure BDA0002652378560000073
wherein, the group R1 is a cyclic hydrocarbon group or an aromatic group containing halogen. In one embodiment, the group R1 is selected from a halogen atom or a halomethyl-substituted cyclobutyl, phenyl, biphenyl, benzhydryl. In other words, in one embodiment, the halogen-containing dianhydride is selected from the following structures substituted with a halogen atom or a halomethyl group:
Figure BDA0002652378560000081
in a more specific embodiment, the halogen-containing dianhydride is:
Figure BDA0002652378560000082
the chemical reaction that takes place in this step is:
Figure BDA0002652378560000083
or
Figure BDA0002652378560000084
S4: subjecting the polyimide precursor to intramolecular condensation to form a polyimide film.
In one embodiment, the step S4 includes: and dissolving and filtering the polyamic acid precursor, coating the filtrate on a glass substrate, placing at high temperature under vacuum to remove the solvent, baking at high temperature to form a film, soaking in deionized water, separating and drying from the glass substrate to obtain the polyimide film.
The chemical reaction that takes place in this step is:
Figure BDA0002652378560000091
or
Figure BDA0002652378560000092
In this step, the temperature profile of the polyimide film cured is as shown in any one of fig. 1(a) to 1(d) below. The cross-linking curing process of the polyimide film lasts for 3-5 h; the temperature rising speed is 4-10 ℃, and the highest temperature is 420-500 ℃. The baking stage is divided into a hard baking mode and a soft baking mode. The hard baking is directly heating to the highest temperature and cooling for about 1h, as shown in fig. 1(a) and fig. 1 (b). The soft baking includes two or more temperature increases, each temperature increase is followed by a constant temperature for a period of time, for example, 20 minutes to 40 minutes, and finally the temperature decrease is performed again, so as to achieve the cross-linking and solvent removal of the material in different constant temperature stages, as shown in fig. 1(c) and fig. 1 (d). It is understood that the methods used herein include, but are not limited to, the above-described baking modes and time intervals.
The method for producing a polyimide film of the present application produces a polyimide film using a diamine containing a porphine nickel (II) structure as a raw material. When porphine nickel (II) is catalytically hydrogenated in a common solvent, porphine nickel (II) is preferentially hydrogenated, but the benzene ring is preferentially hydrogenated in trifluoroacetic acid. According to the preparation method, a nitrating agent is introduced into trifluoroacetic acid to synthesize nitrated porphin nickel (II), diamine containing porphin nickel (II) is prepared by using hydrazine salt, then a dianhydride structure containing halogen is introduced to generate a polyimide precursor, and the polyimide precursor is subjected to crosslinking and curing at high temperature, so that the polyimide film material with excellent heat resistance, mechanical property and optical property is finally obtained.
The present application also provides a polyimide film, which can be prepared using the above preparation method. The polyimide film is selected from the following compounds:
Figure BDA0002652378560000101
or
Figure BDA0002652378560000102
Wherein the group R is selected from-H, alkyl, alkoxy, alkenyl, carbonyl, carboxyl, hydroxyl, amido, halogen, biphenyl, heterocyclic radical, phenyl or tolyl.
In one embodiment, the group R1 is a halogen-containing cycloalkyl, aryl group.
In one embodiment, the group R1 is selected from a halogen atom or a halomethyl-substituted cyclobutyl, phenyl, biphenyl, benzhydryl.
In a more specific embodiment of the method of the present invention,
the polyimide is as follows:
Figure BDA0002652378560000111
or
Figure BDA0002652378560000112
The polyimide film and the method for producing the same of the present application will be described below with reference to specific examples.
1. Example 1
Example 1 comprises the following steps:
1.1 preparation of dinitroporphine Nickel (II)
The porphine nickel (II) used in example 1 is 5,10,15, 20-tetramethyl-21H, 23H-porphine nickel (II), which is commercially available.
Under the protection of argon, 0.3-1.1 mol of 5,10,15, 20-tetramethyl-21H, 23H-porphine nickel (II) is added into a reaction container, then trifluoroacetic acid solvent with the volume of 12-50 mL is added for dissolving, stirring is carried out continuously, and 0.1-2.5 mol of sodium nitrite completely dissolved by using 2-5 mL of solvent is gradually dripped into the solution. And after reacting for 12-30 min at room temperature, stopping stirring, adding 100mL of deionized water into the reaction solution, fully stirring, standing, extracting by using dichloromethane, collecting an organic layer, and performing rotary evaporation to obtain a crude product. Then, the volume ratio of 5: 3, leaching and rotary evaporating the dichloromethane/petroleum ether mixed solution to obtain a solid, namely para-dinitroporphin nickel (II). The reaction that takes place in this step is:
Figure BDA0002652378560000121
wherein R is methyl.
1.2 preparation of diaminoporphyrin Nickel (II)
Adding para-nitroporphine nickel (II) into a reaction container under the protection of argon, dissolving and stirring with a trifluoroacetic acid solvent with the volume of 10-40 mL, heating to 40-60 ℃, slowly adding 0.1-2.3 mol of hydrazine hydrochloride (2 HN. NH 22 HCl), raising the temperature to 75-100 ℃ after the addition is finished, reacting for 12-30 h, obtaining a crude product after the reaction is finished, carrying out suspended evaporation, further dissolving and filtering with a dichloromethane/ethyl acetate mixed solution with the volume ratio of 8: 1-12: 1, and further carrying out suspended evaporation on the obtained filtrate to obtain para-nitroporphine nickel (II).
The reactions that occur in this step are:
Figure BDA0002652378560000122
1.3 preparation of polyimide precursors
The halogen-containing dianhydride used in example 1 may be fluorine-containing dianhydride, specifically:
Figure BDA0002652378560000131
which can be purchased commercially.
Firstly, 1-5.7 mol of para-diaminoporphyrin nickel (II) and N-methylpyrrolidone solvent are added into a round bottom flask with argon protection. Wherein the addition amount of the solvent is 10-200 mL until the para-diaminoporphyrin nickel (II) is fully dissolved, and the volume of the reference solvent is 10-200 mL. And (3) after the para diamino porphine nickel (II) is completely dissolved, adding 0.5-9.5 mol of the fluorine-containing dianhydride monomer, and continuously stirring at normal temperature to react for 24-96 h to obtain a polyimide precursor, namely the polyamic acid containing the porphine nickel (II) structure.
The chemical reaction that takes place in this step is:
Figure BDA0002652378560000132
1.4 preparation of polyimide films
Dissolving the obtained polyimide precursor in 10-135ml of methyl pyrrolidone, filtering the polyamic acid solution by using an organic filter membrane, suspending the obtained filtrate on a glass substrate, keeping the temperature constant for 0.5-1 h at 80 ℃ in a vacuum environment, and removing 70% of NMP solvent. Heating under vacuum readily removed the solvent NMP. And then sending the polyimide film into a high-temperature muffle furnace, baking at 450-475 ℃, and performing crosslinking and curing to obtain the polyimide film. The temperature profile of the baking can be referred to fig. 1(a) to 1(d), and in the present embodiment, the baking is performed using the temperature profile of fig. 1 (a). And then soaking the whole glass plate and the film in deionized water for 72-96 h to enable the polyimide film to be freely taken off, and drying at 80 ℃ to finally obtain the polyimide film.
In this step, the polyimide precursor undergoes intramolecular condensation and is cured to form a film. Specifically, the chemical reaction that takes place in this step is:
Figure BDA0002652378560000141
referring to the nuclear magnetic spectrum of fig. 2, the polyimide film of example 1 was successfully synthesized.
2. Example 2
Example 2 comprises the following steps:
2.1 preparation of dinitroporphine Nickel (II)
The porphine nickel (II) used in example 2 is 5,10,15, 20-tetramethyl-21H, 23H-porphine nickel (II), which is commercially available.
Under the protection of argon, adding 0.3-1.1 mol of 5,10,15, 20-tetramethyl-21H, 23H-porphine nickel (II) into a reaction vessel, then adding 12-50 mL of trifluoroacetic acid solvent for dissolving, continuously stirring, and adding 2-5 mL of sodium nitrite which is completely dissolved by using 2-2.5 mol into the solution at one time. And after reacting for 12-30 min at room temperature, stopping stirring, adding 100mL of deionized water into the reaction solution, fully stirring, standing, extracting by using dichloromethane, collecting an organic layer, and performing rotary evaporation to obtain a crude product. Then, the volume ratio of 5: 3, leaching and rotary evaporating the dichloromethane/petroleum ether mixed solution to obtain a solid, namely the ortho-dinitroporphin nickel (II). The reaction that takes place in this step is:
Figure BDA0002652378560000142
wherein R is methyl.
It is to be noted that examples 1 and 2 are different in that sodium nitrite is gradually added dropwise and added once, respectively, depending on the reactive group, thereby obtaining the para-and ortho-dinitrophthalocyanine structures.
2.2 preparation of diaminoporphyrin Nickel (II)
Under the protection of argon, adding ortho-dinitroporphin nickel (II) into a reaction container, dissolving and stirring with a trifluoroacetic acid solvent with the volume of 10-40 mL, heating to 40-60 ℃, slowly adding 0.1-2.3 mol of hydrazine hydrochloride (2HN & NH 22 HCl), raising the temperature to 75-100 ℃ after the addition is finished, reacting for 12-30 h, after the reaction is finished, carrying out suspension evaporation to obtain a crude product, further dissolving and filtering with a dichloromethane/ethyl acetate mixed solution with the volume ratio of 8: 1-12: 1, and further carrying out suspension evaporation on the obtained filtrate to obtain the ortho-dinitroporphin nickel (II).
The reaction that takes place in this step is:
Figure BDA0002652378560000151
2.3 preparation of polyimide precursors
The halogen-containing dianhydride used in example 2 may be fluorine-containing dianhydride, specifically:
Figure BDA0002652378560000152
which can be purchased commercially.
Firstly, 1-5.7 mol of para amino porphine nickel (II)) and N-methyl pyrrolidone are added into a round bottom flask with argon protection. The solvent is added until the para-amino porphine nickel (II) is fully dissolved, and the volume of the solvent is 10-200 mL as a reference. And (3) after para amino porphin nickel (II)) is completely dissolved, adding 0.5-9.5 mol of fluorine-containing dianhydride monomer, and continuously stirring at normal temperature to react for 24-96 h to obtain a polyimide precursor, namely the polyamide acid containing porphin nickel (II) structure.
The chemical reaction that takes place in this step is:
Figure BDA0002652378560000161
2.4 preparation of polyimide films
Dissolving the obtained polyimide precursor in 10-135mL of toluene, filtering the polyamic acid solution by using an organic filter membrane, suspending the obtained filtrate on a glass substrate, keeping the temperature constant for 0.5-1 h at 80 ℃ in a vacuum environment, and removing 70% of the toluene solvent. And then sending the polyimide film into a high-temperature muffle furnace, baking at 450-475 ℃, and performing crosslinking and curing to obtain the polyimide film. The temperature profile of baking can refer to fig. 1(a) to 1(d), and in the present embodiment, baking is performed using the temperature profile of fig. 1 (b). And then soaking the whole glass plate and the film in deionized water for 72-96 h to enable the polyimide film to be freely taken off, and drying at 80 ℃ to finally obtain the polyimide film.
In this step, the polyimide precursor undergoes intramolecular condensation and is cured to form a film. Specifically, the chemical reaction that takes place in this step is:
Figure BDA0002652378560000162
3 Performance test
3.1 tensile Property test
The polyimide films of example 1 and example 2 were respectively subjected to tensile property tests, in which the test temperature of the mechanical test was 25. + -.10 ℃ and the humidity was 40. + -.5%, the test mode was a tensile test (stress-strain curve), the maximum tensile force was 50N, and the tensile speed was 5 mm/min. The test sample was a polyimide film having a diameter of 30mm and a length of 100 mm. As shown in fig. 3, the polyimide film of example 1 had a maximum stress δ F-max of 389MPa and a maximum strain ∈ F-max of 17.4%. The polyimide film of example 2 had a maximum stress δ H-max of 374MPa and a maximum strain ∈ H-max of 16.2%; the specification is better than that required by the current OLED, and the OLED has good mechanical property.
3.2 thermogravimetric Curve test
The weight loss on heat of the polyimide films of examples 1 and 2 was analyzed, and the weight loss on heat curve is shown in fig. 4. The temperature at which the polyimide film of example 1 lost 1% by mass was: t1 ═ 592.1 ℃. The temperature at which the polyimide film of example 2 lost 1% by mass was: t2 ═ 594.8 ℃. Superior to most of the commercial products at present, and the differences of the polyimide films of example 1 and example 2 are small.
3.3 light transmittance test
The light transmittance tests were performed on the polyimide films of examples 1 and 2, respectively, and as shown in fig. 5, the polyimide films of examples 1 and 2 were 80% or more and 85% or more in most of the wavelengths. Meets the permeability requirement (more than 75%) of all flexible panels under the current environment.
Referring to fig. 6, a flexible display panel 100 is further provided in the third embodiment of the present application, which includes a flexible substrate 10, and the flexible substrate 10 includes the polyimide film. The flexible display panel 100 may be, for example, an organic light emitting diode display panel, a micro light emitting diode display panel, or a sub-millimeter light emitting diode display panel. In addition, the flexible display panel 100 may further include a driving circuit layer 20 disposed on the flexible substrate 10 and a light emitting layer 30 disposed on the driving circuit layer 20.
The polyimide film containing the porphine nickel (II) structure has excellent performances in the aspects of heat resistance, mechanical properties and optical properties, and can be suitable for the current flexible display panel.
The foregoing detailed description of the embodiments of the present application has been presented to illustrate the principles and implementations of the present application, and the following detailed description of the embodiments is provided to aid in understanding the present application. Meanwhile, for those skilled in the art, according to the idea of the present application, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present application.

Claims (10)

1. A method for manufacturing a polyimide film, comprising the steps of:
dissolving porphine nickel (II) in trifluoroacetic acid to carry out nitration reaction with a nitrating agent to generate dinitroporphine nickel (II), wherein the porphine nickel (II) is the following compound:
Figure FDA0003598895150000011
wherein the group R is selected from-H, alkyl, alkoxy, alkenyl, carbonyl, carboxyl, hydroxyl, amido, halogen, biphenyl, heterocyclic radical, phenyl or tolyl;
reacting the dinitroporphine nickel (II) with a hydrazine salt to form diaminoporphine nickel (II);
polymerizing the diaminoporphyrin nickel (II) with a halogen-containing dianhydride to form a polyimide precursor, wherein the halogen-containing dianhydride is the following compound:
Figure FDA0003598895150000012
wherein, the group R1 is a halogen-containing cycloalkyl group or aryl group, and the halogen in the halogen-containing dianhydride and the halogen-containing cycloalkyl group or aryl group is fluorine; and
subjecting the polyimide precursor to intramolecular condensation to form a polyimide film.
2. The method for producing a polyimide film according to claim 1, wherein the step of dissolving the porphine nickel (II) in trifluoroacetic acid to cause a nitration reaction with a nitrating agent to produce a dinitroporphine nickel (II) comprises: and (3) dissolving the porphine nickel (II) in a solvent, gradually dropwise adding a nitrating agent, and reacting to generate the para-nitro porphine nickel (II).
3. The method for producing a polyimide film according to claim 1, wherein the step of dissolving the porphine nickel (II) in trifluoroacetic acid to cause a nitration reaction with a nitrating agent to produce a dinitroporphine nickel (II) comprises: dissolving the porphine nickel (II) in a solvent, and adding a nitrating agent at one time to react to generate the ortho-porphine nickel (II).
4. The method for producing a polyimide film according to claim 1, wherein the step of reacting the dinitroporphin nickel (II) with a hydrazine salt to form the diaminoporphyrin nickel (II) comprises: under the protection of argon, dissolving dinitroporphin nickel (II) by using a solvent, heating to 40-60 ℃, slowly adding hydrazine salt, raising the temperature to 75-100 ℃, and reacting for 12-30 h to generate the diamino porphin nickel (II).
5. The method for producing a polyimide film according to claim 1, wherein the group R1 is selected from the group consisting of a halogen atom or a halogenated methyl group-substituted cyclobutyl group, phenyl group, biphenyl group and benzhydryl group.
6. The method of producing a polyimide film according to claim 1, wherein the step of subjecting the polyimide precursor to intramolecular condensation to form a polyimide film comprises: dissolving and filtering the polyimide precursor, coating the filtrate on a glass substrate, placing at high temperature under vacuum to remove the solvent, baking at high temperature to form a film, soaking in deionized water, separating and drying from the glass substrate to obtain the polyimide film.
7. A polyimide film, wherein the polyimide is selected from the group consisting of:
Figure FDA0003598895150000021
or
Figure FDA0003598895150000022
Wherein the group R is selected from-H, alkyl, alkoxy, alkenyl, carbonyl, carboxyl, hydroxyl, amido, halogen, biphenyl, heterocyclic radical, phenyl or tolyl;
the group R1 is a halogen-containing cycloalkyl group or aryl group, wherein the halogen in the halogen-containing cycloalkyl group or aryl group is fluorine.
8. The polyimide film of claim 7, wherein the group R1 is selected from the group consisting of a halogen atom or a halogenated methyl alkyl substituted cyclobutyl, phenyl, biphenyl, benzhydryl.
9. The polyimide film of claim 7, wherein the polyimide is:
Figure FDA0003598895150000031
or
Figure FDA0003598895150000032
10. A flexible display panel characterized in that it comprises a flexible substrate comprising the polyimide film according to any one of claims 7 to 9.
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